Low expansion transparent glass ceramics

ABSTRACT

There are provided low expansion transparent glass-ceramics obtained by heat treating a base glass produced at a relatively low melting temperature of 1530° C. or below. The glass-ceramics have an average linear thermal expansion coefficient within a range from +6×10 −7 /° C. to +35×10 −7 /° C., 80% transmittance wavelength (T 80 ) of 700 nm or below internal transmittance of 75% or over at light wavelength of 1550 nm, heat resisting temperature of 800° C. or over and Young&#39;s modulus of 90 GPa or over. The glass-ceramics comprise SiO 2 , Al 2 O 3 , MgO, CaO, BaO, ZnO, Li 2 O, TiO 2  and ZrO 2  and contain β-quartz or β-quartz solid solution as a predominant crystal phase.

This application is a continuation-in-part of Ser. No. 09/841,614, filed Apr. 24, 2001, which claims priority from Japanese Patent Applications Serial Nos. 2000-206914, filed Jul. 7, 2000; 2000-273411, filed Sep. 8, 2000 and 2001-066304, filed Mar. 9, 2001.

BACKGROUND OF THE INVENTION

This invention relates to low expansion, transparent glass-ceramics.

Known in the art of glass-ceramics are several types of low expansion, transparent glass-ceramics formed by melting and heat treating a base glass of a SiO₂—Al₂O₃—Li₂O system containing a nucleating agent.

For example, U.S. Pat. No. 3,499,773 discloses low expansion transparent glass-ceramics selectively providing a non-transparent portion which is obtained from a base glass of a SiO₂—Al₂O₃—Li₂O system containing one or more of TiO₂, ZrO₂ and SnO₂ as a nucleating agent and optionally a small amount of MgO, CaO, SrO, BaO etc. For manufacturing the glass-ceramics disclosed in this patent, the melting temperature was 1537° C. to 1593° C. (Example 1: 2800° F. to 2900° F.). U.S. Pat. No. 4,341,543 discloses transparent glass-ceramics obtained from a base glass of a SiO₂—Al₂O₃—Li₂O system containing TiO₂ and ZrO₂ as nucleating agents. For manufacturing the glass-ceramics disclosed in this patent, the melting temperature was 1650° C.

In manufacturing these glass-ceramics disclosed in the patent specifications of the above mentioned patents, however, a relatively high temperature is required for melting the base glasses which results in difficulty in producing glass-ceramics having an excellent optical homogeneity in a large scale.

U.S. Pat. No. 3,681,102 describes that glass-ceramics of a SiO₂—Al₂O₃—ZnO system containing spinel crystal as a predominant crystal phase and having an average linear thermal expansion coefficient a within a range from 25×10⁻⁷ to 40×10⁻⁷ were obtained at a melting temperature within a range from 1650° C. to 1800° C. Japanese Patent Application Laid-open Publication No. Hei 11-335139 describes that glass-ceramics of a SiO₂—Al₂O₃—ZnO system containing spinel crystal as a predominant crystal phase and having an average linear thermal expansion coefficient α within a range from 33×10⁻⁷ to 40×10⁻⁷ were obtained at a melting temperature within a range from 1600° C. to 1625° C. These glass-ceramics, however, require a high melting temperature of 1600° C. or over and, moreover, contain gahnite (ZnAl₂O₄) which is known to be a very hard crystal and, therefore, have difficulty in polishing.

Japanese Patent Application Laid-open Publication Nos. Hei 10-321759 and Hei 10-321760 describe that low expansion glass-ceramics were obtained at a relatively low melting temperature. These glass-ceramics, however, are all opaque glass-ceramics and no transparent glass-ceramics were obtained.

An optical waveguide element generally consists of a lower clad, a core and an upper clad disposed on a substrate. SiO₂ clads made of SiO₂ are used for the lower and upper clads, a SiO₂—GeO₂ core made by doping GeO₂ is used for the core, and a Si single crystal wafer or quartz is used for the substrate (Japanese Patent Application Laid-open Publication Nos. Hei 7-113923, Hei 11-2733 and 2000-121867).

There is a recent tendency toward seeking higher physical and chemical properties for low expansion transparent glass-ceramics. These properties include:

-   (1) Melting and refining of a base glass should be easy and, for     this purpose, materials of the base glass should not include cord,     foam or inclusion but should have a high optical homogeneity. -   (2) Precipitated crystal should be fine and have excellent     transparency, particularly excellent transmittance in the visible     rays region. -   (3) Materials should not substantially contain Na₂O or K₂O, since,     if the materials contain Na₂O or K₂O, ions of such ingredient     scatter during processing of the glass resulting in difficulties. -   (4) Low expansion transparent glass-ceramics generally contain a     relatively large amount of SiO₂ for achieving required properties     and hence a relatively high melting temperature of 1600° C. or over     is generally required. From the standpoint of manufacturing process     design and quality control, however, a lower melting temperature is     preferable.

In a case where a Si single crystal wafer is used as a substrate for an arrayed waveguide grating (AWG) type planar lightwave circuit using an optical waveguide element, the surface of the substrate is exposed to a temperature exceeding 800° C. in the manufacturing process and, for this reason, deformation or distortion of the substrate takes place due to difference in thermal expansion between the substrate and layers provided on the substrate and such deformation and distortion in turn cause change in light wavelength and impairs flatness of the substrate. Even in a normal state of use, difference in a coefficient of thermal expansion between Si single crystal and SiO₂ produces stress in the arrayed waveguide grating resulting change in refractive index of the arrayed waveguide grating and this necessitates insertion of a wavelength sheet in the center of the arrayed waveguide grating. There is an additional disadvantage in using the Si single crystal as the substrate that adjustment of temperature becomes necessary.

On the other hand, use of quartz as the substrate is disadvantageous, as compared with the Si single crystal, in respect of heat conductivity, mechanical properties and easiness of processing.

It is, therefore, an object of the invention to eliminate the above described disadvantages of the prior art technique and dissolve the problem that glass-ceramics which may overcome such disadvantages require a high melting temperature.

It is another object of the invention to provide low expansion transparent glass-ceramics which can be obtained at a relatively low melting temperature, more specifically 1530° C. or below.

It is another object of the invention to provide an optical waveguide element, more particularly an arrayed waveguide grating (AWG) type planar lightwave circuit, employing such low expansion transparent glass-ceramics which can maintain necessary properties in a hybrid integrated circuit and can be manufactured at a low cost.

SUMMARY OF THE INVENTION

Accumulated studies and experiments made by the inventors of the present invention for achieving the above described objects of the invention have resulted in the finding, which has led to the present invention, that low expansion transparent glass-ceramics and glass-ceramic substrates which have an average linear thermal expansion coefficient (α) within a range from +10×10⁻⁷/° C. to +35×10⁻⁷/° C. within a temperature range from 100° C. to 300° C., have an excellent optical homogeneity for the reason that materials of a base glass can be melted at a low melting temperature of 1530° C. or below, and also have improved transparency which is represented by 80% transmittance wavelength (T₈₀) of 700 nm or below can be obtained from a SiO₂—Al₂O₃—Li₂O base glass containing TiO₂ and ZrO₂ as nucleating agents and further containing MgO, CaO, SrO, BaO or ZnO in specific amounts.

For achieving the above described objects of the invention, there are provided low expansion transparent glass-ceramics obtained by heat treating a base glass produced at a melting temperature of 1530° C. or below, said glass-ceramics containing β-quartz or β-quartz solid solution as a predominant crystal phase and 50%–60% SiO₂ in mass % on the basis of amount of total oxides, being free of K₂O and Na₂O, having an average linear thermal expansion coefficient (α) within a range from +6×10⁻⁷/° C. to +35×10⁻⁷/° C. within a temperature range from 100° C. to 300° C. and having 80% transmittance wavelength (T₈₀) of 700 nm or below.

In one aspect of the invention, the glass-ceramics comprise in mass % on the basis of amount of total oxides:

Al₂O₃  20–30% MgO 0.5–2% CaO 0.5–2% SrO   0–10% BaO   1–5% ZnO 0.5–15% Li₂O 1.5–3.5% TiO₂   3–6% ZrO₂   1–5% Nb₂O₅   0–5% La₂O₃   0–5% Y₂O₃   0–5% As₂O₃ and/or Sb₂O₃   0–2%.

In another aspect of the invention, there are provided low expansion transparent glass-ceramics obtained by heat treating a base glass produced at a melting temperature of 1530° C. or below, said glass-ceramics containing β-quartz or β-quartz solid solution as a predominant crystal phase and 50%–60% SiO₂ in mass % on the basis of amount of total oxides and 1%–5% BaO in mass % on the basis of amount of total oxides, having an average linear thermal expansion coefficient (α) within a range from +6×10⁻⁷/° C. to +35×10⁷/° C. within a temperature range from 100° C. to 300° C. and having 80% transmittance wavelength (T₈₀) of 700 nm or below.

In one aspect of the invention, the low expansion transparent glass-ceramics comprises in mass % on the basis of amount of total oxides:

Al₂O₃  20–30% MgO 0.5–2% CaO 0.5–2% SrO   0–10% ZnO 0.5–15% Li₂O 1.5–3.5% TiO₂   3–6% ZrO₂   1–5% Nb₂O₅   0–5% La₂O₃   0–5% Y₂O₃   0–5% As₂O₃ and/or Sb₂O₃   0–2%.

In another aspect of the invention, there are provided low expansion transparent glass-ceramics obtained by heat treating a base glass produced at a melting temperature of 1530° C. or below, said glass-ceramics containing 50%–60% SiO₂ in mass % on the basis of amount of total oxides and 1.5%–3.5% Li₂O on the basis of amount of total oxides, being free of K₂O and Na₂O, having an average linear thermal expansion coefficient (α) within a range from +6×10⁻⁷/° C. to +35×10⁻⁷/° C. within a temperature range from 100° C. to 300° C. and having 80% transmittance wavelength (T₈₀) of 700 nm or below.

In another aspect of the invention, the glass-ceramics comprise in mass % on the basis of amount of total oxides:

Al₂O₃  20–30% MgO 0.5–2% CaO 0.5–2% SrO   0–10% BaO   1–5% ZnO 0.5–15% TiO₂   3–6% ZrO₂   1–5% Nb₂O₅   0–5% La₂O₃   0–5% Y₂O₃   0–5% As₂O₃ and/or Sb₂O₃   0–2%.

In another aspect of the invention, there are provided low expansion transparent glass-ceramics obtained by heat treating a base glass produced at a melting temperature of 1530° C. or below, said glass-ceramics containing 50%–60% SiO₂ in mass % on the basis of amount of total oxides, 1.5%–3.5% Li₂O on the basis of amount of total oxides and 1%–5% BaO in mass % on the basis of amount of total oxides, having an average linear thermal expansion coefficient (α) within a range from +6×10⁻⁷/° C. to +35×10⁻⁷/° C. within a temperature range from 100° C. to 300° C. and having 80% transmittance wavelength (T₈₀) of 700 nm or below.

In another aspect of the invention, the glass-ceramics comprise in mass % on the basis of amount of total oxides:

Al₂O₃  20–30% MgO 0.5–2% CaO 0.5–2% SrO   0–10% ZnO 0.5–15% TiO₂   3–6% ZrO₂   1–5% Nb₂O₅   0–5% La₂O₃   0–5% Y₂O₃   0–5% As₂O₃ and/or Sb₂O₃   0–2%.

In another aspect of the invention, internal transmittance for a plate having thickness of 10 mm is 75% or over at light wavelength of 1550 nm.

In another aspect of the invention, the low expansion transparent glass-ceramics have a heat resisting temperature of 800° C. or over.

In another aspect of the invention, the low expansion transparent glass-ceramics have Young's modulus of 90 GPa or over.

In another aspect of the invention, amount of eluting lithium ion in the low expansion transparent glass-ceramics is less than 0.0050 μg/cm²

In another aspect of the invention, the low expansion transparent glass-ceramics contain 3%–6% TiO₂ in mass % on the basis of amount of total oxides.

In another aspect of the invention, the low expansion transparent glass-ceramics contain three or more ingredients among RO ingredients (where R is Mg, Ca, Sr, Ba or Zn) in an amount of 0.5% or over in mass % on the basis of amount of total oxides for respective ingredients.

In another aspect of the invention, the low expansion transparent glass-ceramics contain ZnO in a larger amount than other RO ingredients in mass % on the basis of amount of total oxides.

In another aspect of the invention, the low expansion transparent glass-ceramics contain a total amount of the RO ingredients of 3.5% or over in mass % on the basis of amount of total oxides.

In another aspect of the invention, the low expansion transparent glass-ceramics contain a total amount of R′O ingredients (where R′ is Mg, Ca, Ba or Sr) of 3%–13% in mass % on the basis of amount of total oxides.

DETAILED DESCRIPTION OF THE INVENTION

Description will be made first about average linear thermal expansion coefficient within the temperature range from 100° C. to 300° C. of the low expansion transparent glass-ceramics of the present invention.

In relation to average linear thermal expansion coefficient of SiO₂, the average linear thermal expansion coefficient of the low expansion glass-ceramics of the present invention preferably is within a range from +6×10⁻⁷/° C. to +35×10⁻⁷/° C. and, more preferably, within a range from +10×10⁻⁷/° C. to +30×10⁻⁷/° C. In a case where a substrate made of transparent glass-ceramics is directly joined to a silicon substrate, the average linear thermal expansion coefficient of the transparent glass-ceramics preferably is in the same range as silicon, that is, the range from +30×10⁻⁷/° C. to +35×10⁻⁷/° C. In a case where an amorphous silicon thin film is deposited on a transparent glass-ceramic substrate by vapor deposition, the average linear thermal expansion coefficient of the transparent glass-ceramics preferably is within a range from +15×10⁻⁷/° C. to +25×10⁻⁷/° C. In a case where transparent glass-ceramics are used for a substrate of an arrayed waveguide grating (AWG) type planar lightwave circuit, the average linear thermal expansion coefficient of the transparent glass-ceramics preferably is within a range from +20×10⁻⁷/° C. to +30×10⁻⁷/° C. In cases where transparent glass-ceramics are used in the field of semi-conductors as a substitute for synthetic quartz and where the transparent glass-ceramics are used as a substrate of a polarization non-dependent AWG type planar lightwave circuit or an athermal AWG type planar lightwave circuit, the average linear thermal expansion coefficient of the transparent glass-ceramics preferably is within a range from +10×10⁻⁷/° C. to +35×10⁻⁷/° C., more preferably within a range from 10×10⁻⁷/° C. to +25×10⁻⁷/° C., and most preferably within a range from +10×10⁻⁷/° C. to +20×10⁷/° C.

The low expansion transparent glass-ceramics of the present invention have excellent homogeneity and transparency. The 80% transmittance wavelength (T₈₀) of the low expansion transparent glass-ceramics of the present invention preferably is 700 nm or below, more preferably, 610 nm or below and most preferably 580 nm or below. The 80% transmittance wavelength (T₈₀) herein means light wavelength on the shortest wavelength side corresponding to transmittance of 80% in the wavelength dependent measurement of transmittance in a sample which has been polished on both surfaces to thickness of 10 mm. Internal transmittance for a plate having thickness of 10 mm preferably is 84% or over at light wavelength of 500 nm and 98% or over at light wavelength of 980 nm. Particularly, since light in the vicinity of 1550 nm is used for a substrate of an optical waveguide for an arrayed waveguide grating (AWG) type planar lightwave circuit in the field of telecommunication, internal transmittance of a plate having thickness of 10 mm preferably is 75% or over. Refractive index of the glass-ceramics preferably is 1.46–1.58 and, more preferably, 1.47–1.57 at light wavelength of 1550 nm.

The low expansion transparent glass-ceramics of the present invention preferably have heat resisting temperature of 800° C. or over. The heat resisting temperature of 800° C. or over herein means that the specimen is not broken when the specimen is heated quickly in an electric furnace in which temperature is set at 800° C. and, after being kept at that temperature for a sufficient length of time, is dropped into water. The low expansion transparent glass-ceramics of the present invention more preferably has heat-resisting temperature of 950° C. The heat resisting temperature of 950° C. or over herein means that the specimen is not broken when the specimen is heated quickly in an electric furnace in which temperature is set at 950° C. and, after being kept at that temperature for sufficient length of time, is dropped into water.

The low expansion transparent glass-ceramics of the present invention preferably have Young's modulus of 90 GPa or over for enabling precision processing of the glass-ceramics.

In one aspect of the invention, the low expansion transparent glass-ceramics of the present invention contain β-quartz or β-quartz solid solution as a predominant crystal phase. “Predominant crystal phase” herein means a crystal phase which is essential for forming a preferred embodiment of the low expansion transparent glass-ceramics of the present invention and is included in a larger amount than any other crystals. β-quartz solid solution means a solid solution crystal in which β-quartz is partly mixed with or replaced by different atoms. β-quartz solid solution includes β-eucryptite (Li₂O—Al₂O₃-2SiO₂) and β-eucryptite solid solution in which β-eucryptite is partly mixed with or replaced by other oxide or oxides including MgO and ZnO. For maintaining the melting temperature at a low level and facilitating polishing, composition of a base glass and crystallizing conditions should be properly selected so as not to include spinel crystal, particularly gahnite.

The low expansion transparent glass-ceramics of the present invention preferably contain SiO₂, Al₂O₃, MgO, CaO, BaO, ZnO, Li₂O, TiO₂ and ZrO₂. A preferable composition range of the glass-ceramics of the present invention will now be described. Amount of each ingredient is expressed in mass % on the basis of amount of total oxides.

The SiO₂ ingredient is a very important ingredient which forms β-quartz or β-quartz solid solution as a predominant crystal phase by heat treating a base glass. This ingredient preferably is contained in an amount of 50% or over for preventing crystal grains from becoming coarse and securing excellent transparency. This ingredient preferably is contained in an amount not exceeding 65% for achieving excellent melting and refining properties of the base glass at a relatively low temperature and maintaining optical homogeneity of the glass-ceramics. A preferable range of this ingredient is up to 60%.

The Al₂O₃ ingredient is a very important ingredient in that it is a component of β-quartz solid solution and serves to lower the melting temperature by adding this ingredient in a relatively large amount. For sufficiently lowering the melting temperature and achieving glass-ceramics which are homogeneous and free from opaqueness, 20% or more of this ingredient should preferably be included and the amount of this ingredient should preferably not exceed 30% for preventing deterioration in the melting property and resistance to devitrification.

In the glass-ceramics of the present invention, the amount and the composition ratio of RO (where R is Mg, Ca, Ba, Sr or Zn) ingredient are important in that this ingredient significantly improves melting property of the base glass and optical homogeneity of the glass-ceramics without impairing transparency. For securing these effects, total amount of the RO ingredients preferably is 3.5% or over, more preferably 6% or over and, most preferably, 7% or over. The total amount of the RO ingredients preferably is 25% or below, more preferably 20% or below and, most preferably, 15% or below.

The ZnO ingredient is the most important ingredient of the RO ingredients. It is therefore preferable that the ZnO ingredient should be contained in a larger amount than the other RO ingredients. For realizing the above described effects of the RO ingredients, the amount of the ZnO ingredient preferably is 0.5% or over, more preferably 2% or over and, most preferably, 3% or over. However, for preventing deterioration in the melting property and resistance to devitrification of the base glass and facilitating maintaining of optical homogeneity of the glass-ceramics, the amount of the ZnO ingredient preferably is 15% or below, more preferably 13% or below and, most preferably, 11% or below.

In the glass-ceramics of the present invention, it is preferable to contain plural RO ingredients for lowering the melting temperature of the base glass. It is therefore preferable to contain three or more different RO ingredients and, more preferably, four or more different RO ingredients in an amount of 0.5% or over for each ingredient.

For lowering the melting temperature of the base glass, it is preferable for the glass-ceramic of the present invention to contain R′O ingredients (where R′ is Mg, Ca, Ba or Sr) in a total amount of 3% or over. It is also preferable to contain R″ ingredients (where R″O is Mg, Ca or Ba) in a total amount of 3% or over.

For achieving the above described effects sufficiently, an amount of the MgO ingredient preferably is 0.5% or over and, for preventing deterioration in transparency of the glass-ceramics, preferably is 2% or below. For achieving the above described effects sufficiently, an amount of the CaO ingredient preferably is 0.5% or over and, for preventing deterioration in transparency of the glass-ceramics, preferably is 2% or below. The SrO ingredient may be added in an amount not exceeding 10%. For achieving the above described effects sufficiently, an amount of the BaO ingredient preferably is 1% or over and, for preventing deterioration in the melting property and resistance to devitrification of the base glass and facilitating maintaining of optical homogeneity of the glass-ceramics, preferably is 5% or below.

For preventing deterioration in the melting property and resistance to devitrification of the base glass and facilitating maintaining of optical homogeneity of the glass-ceramics, a total amount of the R′O ingredients preferably is 3–13%, and more preferably 3–5% or 6–13%. The amount of the ZnO ingredient preferably is 0.5–15% and more preferably 0.5–5% or 6–10%. The ratio of the total amount of the R′O ingredients to the amount of the ZnO ingredient preferably is 0.3–2.0 and more preferably 0.30–0.67 or 0.8–2.0.

The Li₂O ingredient is an important ingredient which, with SiO₂ and Al₂O₃, constitutes β-quartz solid solution. For preventing deterioration in the melting property of the base glass and facilitating maintaining of optical homogeneity of the glass-ceramics or facilitating precipitation of a required amount of fine crystals, the amount of the Li₂O ingredient preferably is 1.5% or over. For preventing crystal grains from becoming coarse and improving transparency of the glass-ceramics, the amount of the Li₂O ingredient preferably is 3.5% or below and more preferably less than 3.5%. For avoiding troubles caused by elution of alkali ions, the amount of the Li₂O ingredient preferably is 3.0% or below and more preferably less than 3.0% and most preferably 2.7% or below. The amount of eluting lithium ions preferably is less than 0.0050 μg/cm², more preferably less than 0.0045 μg/cm² and most preferably less than 0.0040 μg/cm².

The TiO₂ ingredient is an important ingredient which adjusts the thermal expansion coefficient and also functions as a nucleating agent. For achieving required thermal expansion coefficient, the amount of the TiO₂ ingredient preferably is 3% or over and more preferably 3.5% or over. For preventing deterioration in resistance to devitrification of the base glass and facilitating maintaining of optical homogeneity and improving transparency of the glass-ceramics, the amount of the TiO₂ ingredient preferably is 6% or below.

The ZrO₂ ingredient functions as a nucleating agent. For precipitating a desired crystal, the amount of the ZrO₂ ingredient preferably is 1% or over. For preventing deterioration in resistance to devitrification of the base glass and easily maintaining optical homogeneity and improving transparency of the glass-ceramics, the amount of the ZrO₂ ingredient preferably is 5% or below.

The Nb₂O₅, La₂O₃ and Y₂O₃ ingredients are ingredients which, by introducing into the glass-ceramics with the RO ingredients, have been found to improve the melting property of the base glass and significantly improve transparency and optical homogeneity of the glass-ceramics. Addition of an excessive amount of these ingredients, however, deteriorates the melting property of the base glass and impairs homogeneity of the glass-ceramics. The amount of each of these ingredients therefore preferably is 5% or below and more preferably 3% or below. The total amount of the Nb₂O₅, La₂O₃ and Y₂O₃ ingredients preferably is 5% or below and more preferably 3% or below.

For obtaining homogeneous glass-ceramics, the As₂O₃ and/or Sb₂O₃ ingredient may be added as a refining agent in melting glass materials. A total amount of these ingredients up to 2% will suffice.

Other ingredients may be added within a range not impairing desired properties of the glass-ceramics of the present invention. For example, one or more of B₂O₃, GeO₂, F₂, Gd₂O₃ and SnO₂ may be added up to total amount of 5%. As to P₂O₅, it is preferable not to add this oxide for producing the low expansion transparent glass-ceramics with the desired quality in a stable manner.

The low expansion transparent glass-ceramics of the present invention preferably do not contain alkali ingredients other than Li₂O. It is particularly preferable not to substantially contain Na₂O or K₂O. Particularly in manufacturing a planar lightwave circuit such as an arrayed waveguide grating (AWG) type planar lightwave circuit developed in recent telecommunication technology, utilization of semi-conductor equipment is necessary and scattering of alkali ions poses a serious problem.

The low expansion transparent glass-ceramics of the present invention can be manufactured by melting glass materials comprising in mass % on the basis of amount of total oxides:

SiO₂  50–65% Al₂O₃  20–30% MgO 0.5–2% CaO 0.5–2% SrO   0–10% BaO   1–5% ZnO 0.5–15% Li₂O 1.5–3.5% TiO₂   3–6% ZrO₂   1–5% Nb₂O₅   0–5% La₂O₃   0–5% Y₂O₃   0–5% As₂O₃ and/or Sb₂O₃   0–2% at a melting temperature of 1530° C. or below, cooling molten glass materials to provide a base glass, and heat treating the base glass to cause fine β-quartz crystal or β-quartz solid solution crystal to precipitate in the glass matrix. The crystal grain diameter may be set within a range from 0.001 μm to 0.1 μm. For achieving excellent transparency and easiness in polishing, the crystal grain diameter preferably is 0.001 μm–0.1 μm and more preferably 0.001 μm–0.01 μm. By properly adjusting composition of the base glass and conditions for crystallization, glass-ceramics in which fine crystals are scattered in glass matrix and which has desired thermal expansion characteristic in addition to properties suitable for a substrate of a planar lightwave circuit such as high optical homogeneity, transparency, heat resisting property, mechanical strength, easiness in polishing and etching can be produced.

In heat treating the base glass to cause β-quartz or β-quartz solid solution to precipitate, it is preferable to heat treat the base glass in two stages, i.e., heat treat the base glass at 680° C.–730° C. for 2 to 10 hours for nucleation and thereafter heat treat the base glass further at 740° C.–790° C. for 2 to 10 hours for crystallization.

The low expansion transparent glass-ceramics of the present invention can be used as substrates for optical waveguide elements such as an arrayed waveguide grating (AWG) type planar lightwave circuit. For example, the glass-ceramics can be formed to a wafer having a diameter of about 25.4 mm–254 mm and thickness of about 0.5 mm–2.0 mm and polished easily to desired surface roughness and flatness.

The optical waveguide element of the present invention can be produced by providing a core on a substrate consisting of the above described low expansion transparent glass-ceramics and covering the core with a clad which has a smaller refractive index than the core. In a case where refractive index of the glass-ceramic substrate is smaller than that of the clad, the core and clad may be provided directly on the glass-ceramic substrate.

In a case where refractive index of the glass-ceramic substrate is larger than that of the clad, a lower clad may be provided on the glass-ceramic substrate and the core and an upper clad may be provided on the lower clad. Since the low expansion transparent glass-ceramic substrate of the present invention has low expansion characteristic and transparency in this case also, thickness of the lower clad can be made smaller compared with a case where a substrate is made of Si single crystal and, therefore, processing is facilitated and the manufacturing cost thereby can be saved.

In the optical waveguide element of the present invention, a SiO₂ clad which is made mainly of SiO₂ glass may be used as the clad and a SiO₂—GeO₂ core which is made by doping GeO₂ may be used as the core. Refractive index of the SiO₂ clad may be set at about 1.47–1.48 and refractive index of the SiO₂—GeO₂ core may be set at about 1.47–1.49 by adjusting amount of doping of GeO₂.

The optical waveguide element of the present invention therefore may be made by providing the SiO₂—GeO₂ core on the substrate made of the low expansion transparent glass-ceramics and covering the core with the SiO₂ clad having a smaller refractive index than that of the core. The optical waveguide element of the present invention may also comprise a SiO₂ lower clad, a SiO₂—GeO₂ core and an upper SiO₂ clad respectively provided on the substrate made of the low expansion transparent glass-ceramics.

An arrayed waveguide grating (AWG) type planar lightwave circuit may be made by providing an array waveguide grating, a pair of slab waveguides and a plurality of input and output waveguides on the substrate made of the low expansion transparent glass-ceramics. These waveguides can be formed to a desired pattern by the above described SiO₂—GeO₂ core. For eliminating polarization dependent loss caused by birefringence of the waveguide, a ½ wavelength sheet may be provided in the center of the arrayed waveguide grating. The ½ wavelength sheet may be made, e.g., of polyimide. By properly setting the average linear thermal expansion coefficient of the low expansion transparent glass-ceramics of the present invention within the above described range and thereby eliminating difference in thermal expansion coefficient between the clad and between the core, a polarization non-dependent AWG type planar lightwave circuit in which the ½ wavelength sheet is omitted may be designed. By omitting the process of inserting the wavelength sheet, the costs of manufacture and parts may be saved. Further, since the glass-ceramic substrate of the present invention has a smaller average linear thermal expansion coefficient than the Si single crystal substrate, it can be conveniently applied to an athermal AWG type planar lightwave circuit which can be used without adjustment of temperature.

In the optical waveguide element which is made by hybrid integration of a device on a substrate, the substrate plays the role of a heat sink and, therefore, the substrate should preferably have relatively high heat conductivity k, diffusivity of heat a and specific heat Cp. For this purpose, in the glass-ceramic substrate of the present invention, heat conductivity k preferably is 0.7 W/m·k or over and more preferably 1.2 W/m·k or over, diffusivity of heat a preferably is 0.004 cm²/sec or over and more preferably 0.005 cm²/sec or over, and specific heat Cp preferably is 0.6 kJ/kg·k or over and more preferably 0.7 kJ/kg·k.

The core as a desired waveguide pattern can be made by forming a core film by chemical vapor deposition (CVD) or flame hydrolysis deposition (FHD) and forming it to the core by reactive ion etching (RIE). The clad can be formed by employing film forming methods including chemical vapor deposition (CVD) or flame hydrolysis deposition (FHD). As the CVD method, atmospheric pressure CVD (APCVD) using TEOS ozone, CVD using plasma and low pressure CVD may be used.

As a method for manufacturing the optical waveguide element of the present invention, SiO₂ glass particles and SiO₂—GeO₂ glass particles may be deposited on the substrate of the low expansion glass-ceramics by flame hydrolysis deposition (FHD) to form a SiO₂ lower dad film and a SiO₂—GeO₂ core film, the lower clad film and the core film may be made transparent by heating and thereafter the core may be formed in the form of a desired waveguide pattern by reactive ion etching (RIE) and a SiO₂ upper clad covering the core may be formed by flame hydrolysis deposition (FHD).

The optical waveguide element of the present invention may also be made by depositing SiO₂—GeO₂ glass particles on the substrate of the low expansion transparent glass-ceramics by flame hydrolysis deposition (FHD) to form a SiO₂—GeO₂ core film, and making the glass film transparent by heating. Then, a core may be made in the form of a desired waveguide pattern by reactive ion etching (RIE) and a SiO₂ upper clad covering the core may be made by flame hydrolysis deposition (FHD).

EXAMPLES

Examples of the low expansion transparent glass-ceramics and glass-ceramic substrates of the present invention will now be described in comparison with some comparative examples.

Tables 1 to 5 show compositions, melting temperature of base glass, conditions of crystallization, average linear thermal expansion coefficient (α), 80% transmittance wavelength (T₈₀), internal transmittance, heat resisting property, melting property of base glass and amount of eluting lithium ions of the low expansion transparent glass-ceramics and glass-ceramic substrates of the present invention as well as glass-ceramics and glass-ceramic substrates of the comparative examples. The average linear thermal expansion coefficient was measured by the method for measuring thermal expansion of optical glass according to Japan Optical Glass Industry Standard (JOGIS 08-1975).

In the examples and comparative examples, glass materials were melted at a predetermined melting temperature, the base glass after cooling was heated again for nucleation (condition: 700° C.×5 h) and then for crystallization (condition: 750° C.×5 h) to provide glass-ceramics of Example Nos. 1 to 12 and Comparative Example Nos. 1 to 4. By changing conditions for nucleation and crystallization (heating time was 5 hours respectively), glass-ceramics of Example Nos. 13 to 18 were provided. In the glass-ceramics of Example Nos. 1 to 20 and Comparative Example Nos. 1 and 2, β-quartz solid solution was observed as a predominant crystal phase. In the glass-ceramics of Comparative Example Nos. 3 and 4, gahnite (ZnAl₂O₄) was observed as a predominant crystal phase.

Judgement of the melting property was made by observing melting temperature and time, viscosity and defoaming and refining states with naked eye and considering the results of the observation comprehensively. Ranking was made in three stages of “good” which is represented by the mark ◯, “passable” which is represented by the mark Δ and “not good” which is represented by the mark X.

The heat resisting property was measured by quickly heating a substrate specimen (diameter 65 mm, thickness 0.625 mm) which has been polished on both surfaces in electric furnaces in which the temperature is set at 800° C. and 950° C. respectively, keeping the temperature for two hours and then dropping the substrate specimen into water. The specimen which was not broken under either condition is shown by the mark ◯, the specimen which was broken at 950° C. is shown by the mark Δ and the specimen which was broken at 800° C. is shown by the mark X.

The amount of eluting lithium ions was calculated by packing ultra pure water 80 ml (room temperature) and a disk (diameter 65 mm, thickness 0.625 mm) in a film pack, maintaining the contents at about 30° C. for three hours and measuring eluting lithium ions by ion chromatography.

Table 5 shows physical properties of the transparent glass-ceramics of Example Nos. 5, 12 and 2.

TABLE 1 Composition Examples in mass % 1 2 3 4 5 6 SiO₂ 51.7 52.0 51.2 54.0 54.2 51.2 Al₂O₃ 25.6 25.5 27.5 25.7 25.5 27.5 MgO 1.0 1.0 1.0 1.0 1.0 0.5 SrO BaO 1.0 1.0 1.0 1.0 1.0 1.0 CaO 1.3 1.0 1.5 1.0 1.3 2.0 ZnO 10.7 10.5 8.5 8.5 7.7 8.5 Li₂O 2.2 2.5 2.7 2.5 2.7 2.7 TiO₂ 4.0 4.0 4.1 4.0 4.1 4.1 ZrO₂ 2.0 2.0 2.0 1.8 2.0 2.0 La₂O₃ Y₂O₃ As₂O₃ 0.5 0.5 0.5 0.5 0.5 0.5 Melting temperature (° C.) 1500 1500 1500 1520 1500 1500 Nucleating temperature (° C.) 700 700 700 700 700 700 Crystallization temperature (° C.) 750 750 750 750 750 750 Average linear thermal 30 22 19 28 17 17 Expansion coefficient (10⁻⁷/° C.) (100° C.–300° C.) 80% transmittance 440 505 500 460 480 510 wavelength (nm) Internal transmittance 99.8 99.9 99.9 99.9 99.9 99.9 (1550 nm) (%) Heat resisting property ◯ ◯ ◯ ◯ ◯ ◯ Melting property ◯ ◯ ◯ ◯ ◯ ◯ Amount of eluting lithium ions 0.21 0.23 0.26 0.22 0.25 0.26 (μg/Disk) Amount of eluting lithium ions 0.0031 0.0034 0.0038 0.0033 0.0037 0.0038 (μg/cm²)

TABLE 2 Composition Examples in mass % 7 8 9 10 11 12 SiO₂ 53.4 54.0 54.5 54.5 54.0 54.5 Al₂O₃ 25.6 24.0 24.0 24.0 23.5 24.0 MgO 1.0 1.0 1.0 1.0 0.5 1.0 SrO 2.0 1.5 2.0 2.2 BaO 1.0 1.0 2.0 1.5 2.0 2.0 CaO 1.3 1.3 1.0 1.0 1.5 1.0 ZnO 6.7 6.5 4.0 5.0 4.5 3.8 Li₂O 2.5 2.7 2.5 2.5 2.7 2.5 TiO₂ 4.0 4.0 4.0 4.0 3.8 4.0 ZrO₂ 2.0 2.0 2.0 2.0 1.5 2.0 La₂O₃ 2.0 3.0 2.0 Y₂O₃ 2.0 Nb₂O₅ 2.0 2.0 As₂O₃ 0.5 0.5 1.0 1.0 1.0 1.0 Melting temperature (° C.) 1510 1520 1520 1520 1500 1520 Nucleating temperature (° C.) 700 700 700 700 700 700 Crystallization temperature (° C.) 750 750 750 750 750 750 Average linear thermal 24 19 19 20 22 20 Expansion coefficient (10⁻⁷/° C.) (100° C.–300° C.) 80% transmittance 535 540 580 570 555 585 wavelength (nm) Internal transmittance 99.9 99.9 99.9 99.9 99.9 99.7 (1550 nm) (%) Heat resisting property ◯ ◯ ◯ ◯ ◯ ◯ Melting property ◯ ◯ ◯ ◯ ◯ ◯ Amount of eluting lithium ions 0.24 0.25 0.23 0.22 0.24 0.23 (μg/Disk) Amount of eluting lithium ions 0.0035 0.0037 0.0034 0.0033 0.0035 0.0034 (μg/cm²)

TABLE 3 Composition Examples in mass % 13 14 15 16 17 18 SiO₂ 51.7 52.0 51.2 54.2 54.0 54.5 Al₂O₃ 25.6 25.5 27.5 25.5 24.0 24.0 MgO 1.0 1.0 1.0 1.0 1.0 1.0 SrO 2.2 BaO 1.0 1.0 1.0 1.0 1.0 2.0 CaO 1.3 1.0 1.5 1.3 1.3 1.0 ZnO 10.7 10.5 8.5 7.7 6.5 3.8 Li₂O 2.2 2.5 2.7 2.7 2.7 2.5 TiO₂ 4.0 4.0 4.1 4.1 4.0 4.0 ZrO₂ 2.0 2.0 2.0 2.0 2.0 2.0 La₂O₃ 2.0 Y₂O₃ Nb₂O₅ 2.0 As₂O₃ 0.5 0.5 0.5 0.5 0.5 1.0 Melting temperature (° C.) 1500 1500 1500 1500 1520 1520 Nucleating temperature (° C.) 720 715 720 710 715 720 Crystallization temperature (° C.) 770 760 760 760 765 770 Average linear thermal 25 19 16 15 15 17 Expansion coefficient (10⁻⁷/° C.) (100° C.–300° C.) 80% transmittance 460 540 535 510 510 530 wavelength (nm) Internal transmittance 99.7 99.9 99.8 99.8 99.7 99.8 (1550 nm) (%) Heat resisting property ◯ ◯ ◯ ◯ ◯ ◯ Melting property ◯ ◯ ◯ ◯ ◯ ◯ Amount of eluting lithium ions 0.20 0.21 0.26 0.25 0.24 0.22 (μg/Disk) Amount of eluting lithium ions 0.0030 0.0031 0.0038 0.0037 0.0035 0.0033 (μg/cm²)

TABLE 4 Composition Examples in mass % 19 20 SiO₂ 54.6 54.6 Al₂O₃ 24.0 24.0 MgO 1.0 1.0 SrO 2.0 2.0 BaO 2.0 2.0 CaO 1.0 1.0 ZnO 3.8 3.8 Li₂O 2.5 2.5 TiO₂ 4.0 4.0 ZrO₂ 2.0 2.0 La₂O₃ 2.0 2.0 Y₂O₃ As₂O₃ 1.0 1.0 Melting temperature (° C.) 1520 1520 Nucleating temperature (° C.) 700 700 Crystallization temperature (° C.) 850 900 Average linear thermal 18 17 Expansion coefficient (10⁻⁷/° C.) (100° C.–300° C.) 80% transmittance 580 610 wavelength (nm) Internal transmittance 90.0 82.5 (1550 nm) (%) Heat resisting property ◯ ◯ Melting property ◯ ◯ Amount of eluting lithium ions 0.19 0.17 (μg/Disk) Amount of eluting lithium ions 0.0028 0.0025 (μg/cm²)

TABLE 5 Composition Comparative Examples in mass % 1 2 3 4 SiO₂ 67.7 68.5 58.8 63.0 Al₂O₃ 18.9 18.6 20.4 17.8 MgO 1.1 2.2 5.0 4.2 SrO BaO 0.9 1.2 CaO ZnO 1.6 6.8 5.7 Li₂O 3.5 3.0 TiO₂ 3.0 3.9 3.0 5.0 ZrO₂ 2.0 2.0 5.0 3.0 Na₂O 0.2 K₂O 0.2 Nb₂O₅ As₂O₃ 0.9 0.6 0.5 Melting temperature 1650 1650 1600 1625 (° C.) Nucleating temperature 700 700 700 700 (° C.) Crystallization 750 750 750 750 750 temperature (° C.) Average linear thermal −0.9 −0.9 37.1 33.7 Expansion coefficient (10⁻⁷/° C.) (100° C.–300° C.) Internal transmittance 97.0 97.3 97.5 98.0 (1550 nm) (%) Heat resisting property X X X X Melting property X X X X Amount of eluting 0.39 0.34 0.00 0.00 lithium ions (μg/Disk) Amount of eluting 0.0057 0.0050 0.0000 0.0000 lithium ions (μg/cm²)

TABLE 6 Examples Assessed property 5 12 2 Thermal properties Thermal expansion coefficient 17 20 22 (10⁻⁷/° C.) (30–500° C.) Transition point (° C.) 710 761 700 Yield point (° C.) 826 834 820 Heat conductivity k (W/m · k) 1.3 1.3 1.3 Thermal diffusivity a (cm²/sec) 0.006 0.006 0.006 Specific heat Cp (kJ/kg · k) 0.7 0.7 0.7 Mechanical properties Specific gravity 2.80 2.71 2.82 Young's modulus (GPa) 97.6 96.2 99.0 Coefficient of rigidity (GPa) 38.0 38.6 35.1 Poisson's ratio 0.265 0.247 0.270 Knoop hardness Hk 680 620 720 Vickers hardness Hv 730 660 780 Abrasion rate 55 51 48 Optical properties Refractive index 588 nm 1.58 1.57 1.58 1550 nm 1.56 1.55 1.56 Abbe's number ν d 51.2 50.6 51.5 Internal transmittance(%) 500 nm 84 83 85 (thickness: 10 mm) 980 nm 98 97 99 1550 nm 99.9 99.7 99.9 Chemical properties Waterproof property 0.03 0.00 0.02 (powder method) Acid-proof property (powder method) 0.04 0.04 0.05 Alkali-proof property 0.09 0.10 0.12 (powder method) Electric properties Dielectric loss tangent (×10⁻³) 25° C. 2.5 2.1 3.0 200° C. 1.5 0.9 2.2 Dielectric constant (1 MHz) 25° C. 8.8 9.6 9.7 200° C. 28.0 31.0 32.5 Volume resistance (Ω · cm) 25° C. 6.2 × 10¹³ 3.8 × 10¹³ 3.5 × 10¹³ 200° C. 8.1 × 10⁸  4.8 × 10⁸  4.0 × 10⁸  

1. Low expansion transparent glass-ceramics obtained by heat treating a base glass containing 3–15% ZnO in mass % based on the total amount of oxides present and which is produced at a melting temperature of 1530° C. or below, said glass-ceramics containing β-quartz or β-quartz solid solution as a predominant crystal phase and 50%–60% SiO₂ in mass % on the basis of amount of total oxides, being free of K₂O and Na₂O, having an average linear thermal expansion coefficient (α) within a range from +6×10⁻⁷/° C. to +35×10⁻⁷/° C. within a temperature range from 100° C. to 300° C. and having 80% transmittance wavelength (T₈₀) of 700nm or below.
 2. Low expansion transparent glass-ceramics as defined in claim 1 wherein internal transmittance for a plate having thickness of 10 mm is 75% or over at light wavelength of 1550 nm.
 3. Low expansion transparent glass-ceramics as defined in claim 1 having a heat resisting temperature of 800° C. or over.
 4. Low expansion transparent glass-ceramics as defined in claim 1 having Young's modulus of 90 GPa or over.
 5. Low expansion transparent glass-ceramics as defined in claim 1 containing 1.5%–3.5% Li₂O in mass % on the basis of amount of total oxides.
 6. Low expansion transparent glass-ceramics as defined in claim 1 wherein amount of eluting lithium ion is less than 0.0050 μg/cm².
 7. Low expansion transparent glass-ceramics as defined in claim 1 containing 3%–6% TiO₂ in mass % on the basis of amount of total oxides.
 8. Low expansion transparent glass-ceramics as defined in claim 1 containing three or more ingredients among RO ingredients (where R is Mg, Ca, Sr, Ba or Zn) in an amount amount greater than 3% in mass % on the basis of amount of total oxides for respective ingredients.
 9. Low expansion transparent glass-ceramics as defined in claim 8 containing ZnO in a larger amount than other RO ingredients in mass % on the basis of amount of total oxides.
 10. Low expansion transparent glass-ceramics as defined in claim 8 containing a total amount of the RO ingredients of 3.5% or over in mass % on the basis of amount of total oxides.
 11. Low expansion transparent glass-ceramics as defined in claim 1 containing a total amount of R′O ingredients (where R′ is Mg, Ca, Ba or Sr) of 3%–13% in mass % on the basis of amount of total oxides.
 12. Low expansion transparent glass-ceramics as defined in claim 1 comprising in mass % on the basis of amount of total oxides: Al₂O₃  20–30% MgO 0.5–2% CaO 0.5–2% SrO   0–10% BaO   1–5% ZnO   3–15% Li₂O 1.5–3.5% TiO₂   3–6% ZrO₂   1–5% Nb₂O₅   0–5% La₂O₃   0–5% Y₂O₃   0–5% As₂O₃ and/or Sb₂O₃   0–2%.


13. Low expansion transparent glass-ceramics obtained by heat treating a base glass containing 3%–15% ZnO in mass % based on the total amount of oxides present and which is produced at a melting temperature of 1530° C. or below, said glass-ceramics containing 50%–60% SiO₂ in mass % on the basis of amount of total oxides and 1.5%–3.5% Li₂O on the basis of amount of total oxides, being free of K₂O and Na₂O, having an average linear thermal expansion coefficient (α) within a range from +6×10⁻⁷/° C. to +35×10⁻⁷/° C. within a temperature range from 100° C. to 300° C. and having 80% transmittance wavelength (T₈₀) of 700 nm or below.
 14. Low expansion transparent glass-ceramics as defined in claim 13 wherein internal transmittance for a plate having thickness of 10 mm is 75% or over at light wavelength of 1550 nm.
 15. Low expansion transparent glass-ceramics as defined in claim 13 having a heat resisting temperature of 800° C. or over.
 16. Low expansion transparent glass-ceramics as defined in claim 13 having Young's modulus of 90 GPa or over.
 17. Low expansion transparent glass-ceramics as defined in claim 13 wherein amount of eluting lithium ion is less than 0.0050 μg/cm².
 18. Low expansion transparent glass-ceramics as defined in claim 13 containing 3%–6% TiO₂ in mass % on the basis of amount of total oxides.
 19. Low expansion transparent glass-ceramics as defined in claim 13 containing three or more ingredients among RO ingredients (where R is Mg, Ca, Sr, Ba or Zn) in an amount greater than 3% in mass % on the basis of amount of total oxides for respective ingredients.
 20. Low expansion transparent glass-ceramics as defined in claim 19 containing ZnO in a larger amount than other RO ingredients in mass % on the basis of amount of total oxides.
 21. Low expansion transparent glass-ceramics as defined in claim 19 containing a total amount of the RO ingredients of 3.5% or over in mass % on the basis of amount of total oxides.
 22. Low expansion transparent glass-ceramics as defined in claim 13 containing a total amount of R′ ingredients (where R′ is Mg, Ca, Ba or Sr) of 3%–13% in mass % on the basis of amount of total oxides.
 23. Low expansion transparent glass-ceramics as defined in claim 13 comprising in mass % on the basis of amount of total oxides: Al₂O₃  20–30% MgO 0.5–2% CaO 0.5–2% SrO   0–10% BaO   1–5% ZnO   3–15% TiO₂   3–6% ZrO₂   1–5% Nb₂O₅   0–5% La₂O₃   0–5% Y₂O₃   0–5% As₂O₃ and/or Sb₂O₃   0–2%. 